Biomass plasticizer for vinyl chloride resins

Abstract

To provide a biomass plasticizer for a vinyl chloride-based resin which can impart excellent heat resistance and cold resistance to a molding of a vinyl chloride-based resin composition, and can suppress an emission amount of carbon dioxide by employing a biomass plasticizer obtained from a biomass-derived raw material.SOLUTION: A biomass plasticizer for a vinyl chloride-based resin contains component (A): one kind of 4-cyclohexene-1,2-dicarboxylic acid diester represented by general formula (1) or a mixture of two or more kinds of 4-cyclohexene-1,2-dicarboxylic acid diesters, and component (B): epoxidized vegetable oil, wherein a biomass degree of the component (A) is 50-100%, and a mass ratio of the component (A) to the component (B) is 50-99 mass%: 1-50 mass%. In the formula, R1 and R2 are the same or different, and represent a biomass-derived straight-chain alkyl group having 8 to 14 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a biomass plasticizer for vinyl chloride resins. [Background technology]

[0002] Polyvinyl chloride (PVC) is one of the most common plastics, and its properties, such as low cost and excellent heat resistance, give it a wide range of applications. When using PVC, because it is hard and brittle, plasticizers are usually added to make the PVC more flexible before use.

[0003] As plasticizers used in polyvinyl chloride resins, higher alkyl esters of polybasic acids such as phthalates, adipicates, and trimelliticates derived from petroleum are known, and phthalates were often used due to the balance between price and performance.

[0004] In recent years, with the growing demand for a circular economy, there has been a desire to move away from petroleum-derived materials in the materials sector, and the use of biomass has attracted attention. Biomass is an organic compound produced through photosynthesis from carbon dioxide and water, and by utilizing it, it can be converted back into carbon dioxide and water, making it a so-called carbon-neutral material. Recently, the practical application of biomass chemical products made from these biomass raw materials has been progressing rapidly, and attempts are also being made to manufacture general-purpose chemicals from these biomass raw materials.

[0005] Patent Document 1 discloses isosorbide epoxy diester as a plasticizer for vinyl chloride resin. This plasticizer uses biomass-derived isosorbide and unsaturated fatty acids as raw materials. However, this plasticizer had insufficient performance as a plasticizer for vinyl chloride resin. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2016 / 046490 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The problem that this invention aims to solve is to provide a biomass plasticizer for vinyl chloride resins that can impart excellent heat resistance and cold resistance to molded articles of vinyl chloride resin compositions, and can also reduce carbon dioxide emissions by using a biomass plasticizer composition obtained from biomass-derived raw materials. [Means for solving the problem]

[0008] In view of the current situation, the inventors diligently conducted studies to solve the above problems and found that a biomass plasticizer for vinyl chloride resins containing one or more dicarboxylic acid diesters having a specific structure obtained from biomass-derived raw materials and epoxidized vegetable oil is a biomass plasticizer for vinyl chloride resins having a specific biomass content that can impart excellent heat resistance and cold resistance to molded articles of vinyl chloride resin compositions, thus completing the present invention.

[0009] In other words, the present invention provides a biomass plasticizer for vinyl chloride resins, with the following main points:

[0010] [Section 1] (A) Ingredients: General formula (1) [ka] [In the formula, R 1 and R 2 These represent, either identical or different, linear alkyl groups derived from biomass with 8 to 14 carbon atoms. One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by, and (B) Ingredients: Epoxy vegetable oil A biomass plasticizer for vinyl chloride resins, comprising: The biomass plasticizer for vinyl chloride resins is characterized in that the biomass degree of component (A) is 50 to 100%, and the mass ratio of component (A) to component (B) is 50 to 99% by mass: 1 to 50% by mass.

[0011] [Item 2] The biomass plasticizer for vinyl chloride resins according to [Item 1], wherein component (A) is di-n-octyl 4-cyclohexene-1,2-dicarboxylate.

[0012] [Item 3] The biomass plasticizer for vinyl chloride resins according to [Item 1], wherein component (A) is (a) di-n-octyl 4-cyclohexene-1,2-dicarboxylate, (b) n-octyl n-dodecyl 4-cyclohexene-1,2-dicarboxylate, (c) n-octyl n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, (d) di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, (e) n-dodecyl n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, and (f) di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate.

[0013] [Item 4] In component (A), the total of (a) to (f) is 100 mol%, and The biomass plasticizer for vinyl chloride resins according to [Item 3], wherein (a):(b):(c):(d):(e):(f) = 20.0 to 67.2 mol%: 19.8 to 40.7 mol%: 5.7 to 11.8 mol%: 1.9 to 15.8 mol%: 1.1 to 9.2 mol%: 0.1 to 1.4 mol%.

[0014] [Item 5] In component (A), the total of (a) to (f) is 100 mol%, and (a):(b):(c):(d):(e):(f) = 25.0~64.0 mol%:24.8~38.8 mol%:7.2~11.2 mol%:2.4~15.0 mol%:1.4~8.7 mol%, :0.2~1.3 mol%, a biomass plasticizer for vinyl chloride resins as described in [Item 3] or [Item 4].

[0015] [Section 6] A biomass plasticizer for vinyl chloride resins according to any of [Item 1] to [Item 5], wherein the biomass content of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) is 60 to 100%.

[0016] [Section 7] A biomass plasticizer for vinyl chloride resins according to any of [Item 1] to [Item 6], wherein the biomass content of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) is 65 to 100%.

[0017] [Section 8] The biomass plasticizer for vinyl chloride resins according to any one of [Clause 1] to [Clause 7], wherein the epoxidized vegetable oil is epoxidized soybean oil and / or epoxidized linseed oil.

[0018] [Section 9] A vinyl chloride resin composition characterized by containing a vinyl chloride resin and a biomass plasticizer for vinyl chloride resins as described in any of [Item 1] to [Item 8].

[0019] [Section 10] The vinyl chloride resin composition according to item 9, characterized in that it contains 5 to 200 parts by mass of a biomass plasticizer for vinyl chloride resins described in any of items 1 to 8, per 100 parts by mass of vinyl chloride resin.

[0020] [Section 11] A vinyl chloride resin composition according to item [9] or

[10] , characterized by containing 10 to 100 parts by mass of a biomass plasticizer for vinyl chloride resins described in any of items [1] to [8] per 100 parts by mass of vinyl chloride resin.

[0021] [Section 12] A molded article obtained from a vinyl chloride resin composition according to any of items [9] to

[11] . [Effects of the Invention]

[0022] By replacing the composition of plasticizers for vinyl chloride resins, which are entirely dependent on petroleum-derived plasticizers, with biomass plasticizers for vinyl chloride resins obtained from plant-derived raw materials, the amount of petroleum resources used can be reduced, and the environmental burden can be reduced by suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins. The biomass plasticizer for vinyl chloride resins of the present invention has excellent compatibility with vinyl chloride resins, and therefore has excellent plasticization efficiency and flexibility, can impart excellent heat resistance and cold resistance, and can be suitably used as a plasticizer having a specific biomass content. [Modes for carrying out the invention]

[0023] The biomass plasticizer for vinyl chloride resins of the present invention is (A) Ingredients: General formula (1) [ka] [In the formula, R 1 and R 2 These represent, either identical or different, linear alkyl groups derived from biomass with 8 to 14 carbon atoms. One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by, and (B) Ingredients: Epoxy vegetable oil A biomass plasticizer for vinyl chloride resins containing, It is characterized in that the biomass content of component (A) is 50 to 100%, and the mass ratio of component (A) to component (B) is 50 to 99% by mass: 1 to 50% by mass.

[0024] Regarding the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1), R 1 and R 2 Specific examples thereof include, the same or different, each an n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group derived from biomass, preferably, an n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, and particularly preferably, an n-octyl group, n-dodecyl group, n-tetradecyl group.

[0025] Regarding the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1), R 1 and R 2 When they are the same or different and each is a linear alkyl group having 1 to 7 carbon atoms derived from biomass, the heat resistance (weight loss on volatilization) deteriorates, which is not preferable.

[0026] Regarding the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1), R 1 and R 2 When they are the same or different and each is a linear alkyl group having 15 or more carbon atoms derived from biomass, the cold resistance (flexible temperature) deteriorates, which is not preferable.

[0027] Regarding the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1), R 1 and R 2 For the description method of the mixed group ester in which R 1 is an n-octyl group and R 2 is an n-dodecyl group, it shall be described as 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl in this specification and the claims.

Chemical formula

[0028] Specific examples of 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) include 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, with 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl being preferred.

[0029] Specific examples of mixtures of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) include: a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl and 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl; a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl and 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl; a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl; and 4-cyclohexene A mixture of n-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2- A mixture of di-n-dodecyl dicarboxylates, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, a mixture of di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, a mixture of di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, and di-cyclohexene-1,2-dicarboxylate. A mixture of di-n-decyl cyclohexene-1,2-dicarboxylic acid, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylic acid, di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylic acid, di-n-octyl 4-cyclohexene-1,2-dicarboxylic acid, n-octyl 4-cyclohexene-1,2-dicarboxylic acid, and a mixture of di-n-decyl 4-cyclohexene-1,2-dicarboxylic acid, di-n-octyl 4-cyclohexene-1,2-dicarboxylic acid, n-octyl 4-cyclohexene-1,2-dicarboxylic acid, n-octyl 4-cyclohexene-1,2-dicarboxylic acid, and 4-cyclohexene-1,A mixture of 2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, and a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2-dicarboxylic acid=n-decyl=n-dodecyl, and a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-C A mixture of chlorohexene-1,2-dicarboxylic acid=n-decyl=n-tetradecyl and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl and a mixture of 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-decyl, 4-cyclohexene-1,2- Dicarboxylic acid = n-octyl = n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid di n-decyl, 4-cyclohexene-1,2-dicarboxylic acid = n-decyl = n-dodecyl, and a mixture of 4-cyclohexene-1,2-dicarboxylic acid di n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid di n-octyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di n-dodecyl, 4- A mixture of cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl and 4-cyclohexene-1,2-dicarboxylic acid din-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid din-decyl, 4-cyclohexene-1,2-dicarboxylic acid=n-decyl=n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid=n-decyl=n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid din-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and 4-cyclohexene-1,A mixture of 2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-decyl, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl Examples include 4-cyclohexene-1,2-dicarboxylic acid=n-decyl=n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid=n-decyl=n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and mixtures of 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl.

[0030] Among the specific examples of the above-mentioned mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters, the preferred is a mixture of (a) 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, (b) 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-dodecyl, (c) 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, (d) 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, (e) 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and (f) 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl.

[0031] Among the specific examples of the above mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters, preferably, the total of the diester mixture of (a) to (f) is 100 mol%, and (a):(b):(c):(d):(e):(f) = 20.0~67.2 mol%:19.8~40.7 mol%:5.7~11.8 mol%:1.9~15.8 mol%:1.1~9.2 mol%, :0. The mixture is in the range of 1 to 1.4 mol%, and is particularly preferably a mixture in which the total of the diester mixtures (a) to (f) is 100 mol%, and (a):(b):(c):(d):(e):(f) = 25.0 to 64.0 mol%: 24.8 to 38.8 mol%: 7.2 to 11.2 mol%: 2.4 to 15.0 mol%: 1.4 to 8.7 mol%, and 0.2 to 1.3 mol%.

[0032] One or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) are not limited by their manufacturing method, as long as they satisfy the requirements for plasticizer performance. For example, they can be easily obtained by adding one or more linear aliphatic saturated alcohols derived from biomass with 8 to 14 carbon atoms to a known 4-cyclohexene-1,2-dicarboxylic acid or its anhydride derived from petroleum and / or biomass raw materials and reacting them in an esterification reaction.

[0033] In esterification, water entrainers such as benzene, toluene, xylene, and cyclohexane can be used to promote the distillation of water produced by the reaction.

[0034] Furthermore, during the esterification reaction, oxidative degradation of the diester compound and organic solvent (water entrainer) can generate oxygen-containing organic compounds such as oxides, peroxides, and carbonyl compounds, which can adversely affect heat resistance and weather resistance. Therefore, it is desirable to carry out the reaction under atmospheric pressure or reduced pressure in an inert gas atmosphere such as nitrogen gas or under an inert gas flow. After the esterification reaction is complete, it is recommended to remove excess raw materials by distillation under reduced pressure or atmospheric pressure.

[0035] The diester compound according to the present invention obtained by the above esterification method may subsequently be purified by base treatment (neutralization treatment) as needed, followed by washing with water, liquid-liquid extraction, distillation (reduced pressure, dehydration treatment), adsorption purification treatment, etc.

[0036] There are no particular restrictions on the base used in base treatment, as long as it is a basic compound; for example, sodium hydroxide and sodium carbonate are examples.

[0037] Examples of adsorbents used in adsorption purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. These can be used individually or in combination of two or more as appropriate.

[0038] The above process can be carried out at room temperature, but it can also be done by heating it to around 40-90°C.

[0039] The biomass content of diesters is measured by burning the sample to be measured to generate carbon dioxide, purifying the carbon dioxide in a vacuum line, and then reducing it with hydrogen using iron as a catalyst to produce graphite. This graphite is then processed using a tandem accelerator-based system. 14 It is installed in a dedicated C-AMS device (manufactured by NEC Corporation), 14 The count of C, 13 C's flux ( 13 C / 12 C), 14 C's flux ( 14 C / 12 C) is measured, and from this measurement, the sample carbon relative to standard modern carbon is 14 The percentage of C concentration was calculated. For this measurement, oxalic acid (HOxII), provided by the U.S. National Institute of Standards (NIST), was used as the standard sample.

[0040] From the viewpoint of reducing the use of petroleum resources and mitigating environmental impact, a higher biomass content of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) is preferable, as it reduces the environmental impact by suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins. From the viewpoint of practicality, such as simplicity, the biomass content of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) is preferably 50-100%, more preferably 60-100%, and particularly preferably 65-100%. If the biomass content of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) is less than 50%, its contribution to suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins is small and undesirable.

[0041] Furthermore, maleic anhydride, which is a raw material for 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, can also be produced from biomass-derived furfural by known methods, for example, as described in Y. Tachibana, S. Kimura, K. Kasuya, Sci. Rep., 5, 8249 (2015). The biomass content of the maleic anhydride obtained in this way is 99% or more.

[0042] Furthermore, butadiene, which is a raw material for 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, can also be produced from ethanol derived from biomass raw materials by known methods, for example, as described in Japanese Patent Application Publication No. 2019-090061. The biomass content of the butadiene obtained in this way is 99% or more.

[0043] Using the maleic anhydride and butadiene described above, 4-cyclohexene-1,2-dicarboxylic acid or its anhydride derived from biomass raw materials can be produced, for example, by a known Diels-Alder reaction. The biomass content of the 4-cyclohexene-1,2-dicarboxylic acid or its anhydride obtained in this way is 99% or more.

[0044] The 4-cyclohexene-1,2-dicarboxylic acid diester according to the present invention can be produced by carrying out an esterification reaction of 4-cyclohexene-1,2-dicarboxylic acid or its anhydride derived from biomass raw materials with a linear aliphatic saturated alcohol having 8 to 14 carbon atoms derived from biomass raw materials using a known method. The biomass content of the 4-cyclohexene-1,2-dicarboxylic acid diester obtained in this way is 99% or more.

[0045] Alternatively, instead of using biomass-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, it is also possible to use petroleum-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride produced from petroleum-derived butadiene and petroleum-derived maleic anhydride as raw materials. The biomass content of petroleum-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride is less than 1%.

[0046] Linear aliphatic saturated alcohols derived from biomass raw materials having 8 to 14 carbon atoms can be used as a raw material for one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) by obtaining alcohol mixtures obtained by hydrogenation reduction of fatty acid methyl derived from natural oils such as coconut oil and palm kernel oil. Furthermore, the alcohols obtained by separating and purifying the alcohol mixture by distillation or the like can also be used as a raw material for one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1).

[0047] Linear aliphatic saturated alcohols derived from biomass raw materials having 8 to 14 carbon atoms can be used as raw materials for one or more types of 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1), or a mixture of two or more types. The biomass content of the linear aliphatic saturated alcohols derived from biomass raw materials having 8 to 14 carbon atoms is 99% or higher.

[0048] Instead of using biomass-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, the 4-cyclohexene-1,2-dicarboxylic acid diester according to the present invention can be produced by esterifying petroleum-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride with a linear aliphatic saturated alcohol derived from biomass-derived materials having 8 to 14 carbon atoms using a known method. The biomass content of the 4-cyclohexene-1,2-dicarboxylic acid diester obtained in this way is 67% to 78%.

[0049] The acid value of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) is preferably 0.1 mg KOH / g or less, more preferably 0.05 mg KOH / g or less, and particularly preferably 0.01 mg KOH / g or less. When the acid value is 0.1 mg KOH / g or less, the heat resistance of one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) tends to improve, and within this preferred range, it also has a positive effect on improving the thermal oxidation stability of the biomass plasticizer for vinyl chloride resins of the present invention.

[0050] The epoxidized vegetable oil according to the present invention can be, for example, an epoxidized vegetable oil obtained by epoxidizing a vegetable oil, and examples of epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil are used, preferably epoxidized soybean oil and epoxidized linseed oil, and particularly preferably epoxidized soybean oil. The biomass content of the epoxidized vegetable oil according to the present invention is 99% or more. One or more types of epoxidized vegetable oils according to the present invention may be used.

[0051] The present invention relates to a biomass plasticizer for vinyl chloride resins, characterized by containing one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) having a specific biomass content, and epoxidized vegetable oil, each in a specific mass ratio. In this specification and in the claims, the biomass content is the value measured by the method described in the examples below.

[0052] The mass ratio of component (A) and component (B) contained in the biomass plasticizer for vinyl chloride resins of the present invention is (A):component (B) = 50-99% by mass:1-50% by mass.

[0053] <Vinyl chloride resin> The vinyl chloride resins used in this invention are homopolymers of vinyl chloride or vinylidene chloride, and copolymers of vinyl chloride or vinylidene chloride. Their production methods are conventionally known polymerization methods. For general-purpose vinyl chloride resins, a suspension polymerization method in the presence of an oil-soluble polymerization catalyst is used. For vinyl chloride paste resins, an emulsion polymerization method in an aqueous medium in the presence of a water-soluble polymerization catalyst is used. The degree of polymerization of these vinyl chloride resins is typically 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, heat resistance and other properties tend to decrease, while if it is too high, moldability tends to decrease.

[0054] In the case of copolymers, for example, ethylene, propylene, α-olefins having 2 to 30 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl compounds such as vinyl acetate, vinyl propionate, alkyl vinyl ethers, polyfunctional monomers such as diallyl phthalate, and copolymers of these mixtures with vinyl chloride monomer, ethylene Examples include ethylene-acrylic acid ester copolymers such as ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile-(α-methyl)styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, polymethyl methacrylate, and graft copolymers obtained by grafting vinyl chloride monomer onto mixtures thereof.

[0055] <Vinyl chloride resin composition> The content of the biomass plasticizer for vinyl chloride resins in the vinyl chloride resin composition of the present invention is appropriately selected depending on the application, but is usually 5 to 200 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of vinyl chloride resin. If the amount is less than 5 parts by mass, it is difficult to obtain the desired plasticizing effect, and if it is added in excess of 200 parts by mass, bleeding to the surface of the molded product is severe, and in either case it is undesirable. However, when a filler or the like is added to the above vinyl chloride resin composition, the plasticizer can be added in excess of the above range because the filler itself absorbs oil. For example, if 100 parts by mass of calcium carbonate is added as a filler to 100 parts by mass of vinyl chloride resin, the plasticizer can be added in an amount of about 1 to 500 parts by mass.

[0056] The vinyl chloride resin composition of the present invention can be used in combination with other known plasticizers along with the biomass plasticizer for vinyl chloride resins. Furthermore, additives such as stabilizers, stabilizing aids, antioxidants (anti-aging agents), UV absorbers, hindered amine-based light stabilizers, fillers, diluents, viscosity reducers, viscosity increasers, processing aids, lubricants, antistatic agents, flame retardants, foaming agents, adhesives, and colorants may be added as needed.

[0057] Other plasticizers and additives besides the biomass plasticizer for vinyl chloride resins according to the present invention may be blended together with the biomass plasticizer for vinyl chloride resins, either individually or in combination of two or more as appropriate.

[0058] Known plasticizers that can be used in combination with the biomass plasticizer for vinyl chloride resins according to the present invention include, for example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), and bis(2-ethylhexyl) terephthalate (DOT P), phthalate esters such as bis(2-ethylhexyl) isophthalate (DOIP), aliphatic dibasic acid esters such as di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS), tri-2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM), trimellitate Trimellitic acid esters such as triisodecyl litate (TID™), pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM), phosphate esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol, polyesters with molecular weights of 800 to 4000 synthesized by polyesterization of dibasic acids such as adipic acid with glycols, epoxy esters such as 4,5-epoxy-1,2-cyclohexanedicarboxylic acid di-2-ethylhexyl ester, alicyclic dibasic acid esters such as 1,2-cyclohexanedicarboxylic acid diisononyl (DINCH) and 4-cyclohexene-1,2-dicarboxylic acid di-2-ethylhexyl ester (excluding one or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) according to the present invention), dicapric acid 1.Examples include fatty acid glycol esters such as 4-butanediol, citrate esters such as tributyl acetyl citrate (ATBC), trihexyl acetyl citrate (ATHC), triethylhexyl acetyl citrate (ATEHC), and trihexyl butyryl citrate (BTHC), isosorbide diesters, chlorinated paraffins obtained by chlorinating paraffin wax or n-paraffin, chlorinated fatty acid esters such as chlorinated stearate ester, and higher fatty acid esters such as butyl oleate. When incorporating the above-mentioned plasticizers, the recommended amount is approximately 1 to 100 parts by mass per 100 parts by mass of vinyl chloride resin.

[0059] Examples of stabilizers include metal soap compounds such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate; organotin compounds such as dimethyl tin bis-2-ethylhexyl thioglycolate, dibutyl tin maleate, dibutyl tin bisbutyl maleate, and dibutyl tin dilaurate; and antimony mercaptide compounds. When incorporating stabilizers, the recommended amount of stabilizer per 100 parts by mass of vinyl chloride resin is approximately 0.1 to 20 parts by mass.

[0060] Of the aforementioned stabilizers, the combination of calcium stearate and zinc stearate is most preferred in terms of safety and other factors. The amount to be blended is recommended to be 0.1 to 10 parts by mass, preferably 0.2 to 6 parts by mass, in total per 100 parts by mass of vinyl chloride resin. The blending ratio is not particularly limited as long as it shows a stabilizing effect, but it is usually used in the range of 5:1 to 1:5.

[0061] Examples of stabilizing agents include phosphite compounds such as triphenyl phosphite, monooctyldiphenyl phosphite, and tridecyl phosphite; beta-diketone compounds such as acetylacetone and benzoylacetone; polyol compounds such as glycerin, sorbitol, pentaerythritol, and polyethylene glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; and zeolites. When incorporating stabilizing agents, it is recommended to add approximately 0.1 to 20 parts by mass of the stabilizing agent per 100 parts by mass of the vinyl chloride resin.

[0062] Examples of antioxidants include phenolic compounds such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfuric compounds such as alkyl disulfides, thiodipropionates, and benzothiazoles; phosphoric acid compounds such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl) phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. When incorporating antioxidants, the recommended amount of antioxidant per 100 parts by mass of vinyl chloride resin is approximately 0.2 to 20 parts by mass.

[0063] Examples of UV absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate compounds. When incorporating UV absorbers, the recommended amount of UV absorber per 100 parts by mass of vinyl chloride resin is approximately 0.1 to 10 parts by mass.

[0064] Examples of hindered amine-based light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, and bis(2,2,6,6-tetramethyl-1( Octyloxy)-4-piperidyl) ester and reaction products of 1,1-dimethylethyl hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and higher fatty acids, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate Luboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, poly[{(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}}, dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) Examples include polycondensates of ru-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, and N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine. Furthermore, when incorporating a light stabilizer, the recommended amount of light stabilizer per 100 parts by mass of vinyl chloride resin is approximately 0.1 to 10 parts by mass.

[0065] Examples of fillers include calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, metal oxides such as ferrite, glass, carbon, metal fibers and powders, glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate. When incorporating fillers, it is recommended to use approximately 1 to 100 parts by mass of filler per 100 parts by mass of vinyl chloride resin.

[0066] Examples of diluents include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and low-boiling-point aliphatic and aromatic hydrocarbons. When incorporating a diluent, it is recommended to use approximately 1 to 50 parts by mass of the diluent per 100 parts by mass of the vinyl chloride resin.

[0067] Examples of viscosity reducers include various nonionic surfactants, sulfosuccinate anionic surfactants, surfactant silicone compounds, soybean oil lecithin, monohydric alcohols, glycol ethers, and polyethylene glycols. When a viscosity reducer is added, it is recommended that the amount of the viscosity reducer be approximately 0.1 to 20 parts by mass per 100 parts by mass of vinyl chloride resin.

[0068] Examples of thickening agents include synthetic fine silica, bentonite, ultrafine precipitated calcium carbonate, metal soap, hydrogenated castor oil, polyamide wax, oxidized polyethylene, vegetable oil, granular acid ester surfactants, and nonionic surfactants. When incorporating a thickening agent, it is recommended to use approximately 1 to 50 parts by mass of the thickening agent per 100 parts by mass of vinyl chloride resin.

[0069] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearate amide, ethylenebisstearate amide, butyl stearate, and calcium stearate. When incorporating processing aids, it is recommended to use approximately 0.1 to 20 parts by mass of the processing aid per 100 parts by mass of the vinyl chloride resin.

[0070] Examples of lubricants include silicone, liquid paraffin, paraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid waxes, and higher fatty acid waxes. When incorporating a lubricant, it is recommended to add approximately 0.1 to 10 parts by mass of the lubricant per 100 parts by mass of the vinyl chloride resin.

[0071] Examples of antistatic agents include anionic antistatic agents of the alkyl sulfonate, alkyl ether carboxylic acid, or dialkyl sulfosuccinate type; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; cationic antistatic agents such as quaternary ammonium salts such as alkylamidoamine and alkyldimethylbenzyl types, and organic acid salts or hydrochlorides of alkylpyridinium type; and amphoteric antistatic agents such as alkyl betaine and alkylimidazoline types. When incorporating an antistatic agent, it is recommended to add approximately 0.1 to 10 parts by mass of the antistatic agent per 100 parts by mass of vinyl chloride resin.

[0072] Examples of flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; phosphorus compounds such as cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phosphate; and halogen compounds such as chlorinated paraffin. When incorporating flame retardants, it is recommended that the amount of flame retardant be approximately 0.1 to 20 parts by mass per 100 parts by mass of vinyl chloride resin.

[0073] Examples of blowing agents include organic blowing agents such as azodicarbonamide and oxybisbenzenesulfonyl hydrazide, and inorganic blowing agents such as sodium bicarbonate. When incorporating a blowing agent, it is recommended to add approximately 0.1 to 30 parts by mass of the blowing agent per 100 parts by mass of the vinyl chloride resin.

[0074] Examples of colorants include carbon black, lead sulfide, white carbon, titanium white, lithopone, red ochre, antimony sulfide, chromium yellow, chromium green, phthalocyanine green, cobalt blue, phthalocyanine blue, and molybdenum orange. When incorporating colorants, it is recommended to use approximately 1 to 100 parts by mass of colorant per 100 parts by mass of vinyl chloride resin.

[0075] The vinyl chloride resin composition of the present invention can be obtained by stirring and mixing or melting together the biomass plasticizer for vinyl chloride resins, vinyl chloride resin, and various additives as needed, for example, by handling mixing, or by using stirring and mixing machines such as pony mixers, butterfly mixers, planetary mixers, dissolvers, twin-screw mixers, three-roll mills, mortar mixers, Henschel mixers, Banbury mixers, ribbon blenders, or kneaders such as conical twin-screw extruders, parallel twin-screw extruders, single-screw extruders, cone kneaders, and roll kneaders to obtain a vinyl chloride resin composition in powder, pellet, or paste form.

[0076] <Vinyl chloride resin molded product> The vinyl chloride resin composition of the present invention can be molded into a desired shape by molding using conventionally known methods such as vacuum forming, compression molding, extrusion molding, injection molding, calendering, press molding, blow molding, powder molding, spread coating, dip coating, spray coating, paper casting, extrusion coating, gravure printing, screen printing, slush molding, rotational molding, casting, dip molding, and welding.

[0077] The shape of the molded body is not particularly limited, but examples include rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, or special shapes such as those used for toys or ornaments, such as star-shaped or polygonal shapes.

[0078] <Evaluation of polyvinyl chloride resin molded products> (a) Soft temperature The flexible temperature of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is preferably -25°C or lower, and more preferably -30°C or lower. In this specification, the flexible temperature is the value measured by the method described in the examples below.

[0079] (b) Loss on volatilization The loss by volatilization of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is preferably less than 15%, and more preferably less than 13%. In this specification, loss by volatilization refers to the value measured by the method described in the examples below.

[0080] (c) Heat resistance (sheet coloring) evaluation The heat resistance (sheet coloring) evaluation (170°C, 60 minutes) of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is preferably slightly colored, and more preferably no coloring. In this specification, heat resistance (sheet coloring) refers to the value measured by the method described in the examples below.

[0081] (d) Evaluation of vinyl chloride sheets The evaluation of a vinyl chloride sheet containing a plasticizer for vinyl chloride resins is good if the following conditions are met: flexible temperature of -25°C or lower, loss of volatilization of less than 13%, no sheet coloring; flexible temperature of -30°C or lower, loss of volatilization of less than 15%, no sheet coloring; flexible temperature of -30°C or lower, loss of volatilization of less than 15%, slight sheet coloring; and particularly good if the following conditions are met: flexible temperature of -30°C or lower, loss of volatilization of less than 13%, no sheet coloring.

[0082] The vinyl chloride sheet containing the biomass plasticizer for vinyl chloride resins of the present invention is useful as a biomass plasticizer for vinyl chloride resins because it has a low flexibility temperature, low loss on volatilization (170°C, 120 minutes), no coloration in the sheet, and a specific biomass content. [Examples]

[0083] The present invention will be further described in detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations for the compounds in the examples and comparative examples, and the measurements of each property are as follows.

[0084] <Compound used> • 4-Cyclohexene-1,2-dicarboxylic acid anhydride: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Ricacid TH" (biomass content: less than 1%) n-Octanol: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Conol 10WS" (biomass content: 99% or more) n-Dodecanol: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Conol 20P" (biomass content: 99% or more) • n-Tetradecanol: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Conol 1495" (biomass content: 99% or more) • Epoxy-processed soybean oil: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Sansosizer E-2000H" (biomass content: 99% or higher) • Polyvinyl chloride resin: Manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd., product name "Zest1000Z" (straight, degree of polymerization 1050) • DOP: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Sanso-Sizer DOP" (di-2-ethylhexyl phthalate) (biomass content: less than 1%) • DINP: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Sanso-Sizer DINP" (diisononyl phthalate) (biomass content: less than 1%) • DOTH: Manufactured by Shin-Nippon Rika Co., Ltd., product name "Sanso-Sizer DOTH" (4-cyclohexene-1,2-dicarboxylate di2-ethylhexyl) (biomass content: less than 1%)

[0085] (1) Evaluation of diester properties One or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) according to the present invention, obtained in the following production examples, were analyzed by the following method. Acid value: Measured in accordance with JIS K-0070 (1992). Hue: Measured in accordance with JIS K-4101 (Hazen) (1995).

[0086] (2) Gas chromatography analysis (hereinafter abbreviated as GC analysis) Model: Gas chromatograph GC-2025 (manufactured by Shimadzu Corporation) Detector: FID Column: Capillary column ZB-130m Column temperature: Increased from 60°C to 290°C, heating rate = 13°C / min, held for 23 minutes. Carrier gas: Helium Split ratio: 1:80 Sample: 50% acetone solution Injection volume: 0.5μl Determination: DOP was used as an internal standard for quantification.

[0087] (3) Preparation of polyvinyl chloride press sheet 100 parts by mass of polyvinyl chloride resin (straight, degree of polymerization 1050, trade name "Zest1000Z", manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd.) were mixed with 0.3 parts by mass of calcium stearate (manufactured by Nacalai Tesque Co., Ltd.) and 0.2 parts by mass of zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) as stabilizers. After stirring and mixing in a mortar mixer, 50 parts by mass of plasticizer were added and the mixture was handled and mixed until uniform to obtain a polyvinyl chloride resin composition. This resin composition was melt-kneaded using a 5 x 12 inch double roll at 160-166°C for 4 minutes to create a roll sheet. Subsequently, press molding was performed at 162-168°C for 10 minutes to produce a press sheet with a thickness of approximately 1 mm.

[0088] <Evaluation of physical properties of polyvinyl chloride resin molded articles> (4) Tensile properties: The 100% modulus, breaking strength, and breaking elongation of the press sheet were measured in accordance with JIS K-6723 (1995). A smaller 100% modulus value indicates better flexibility, while breaking strength and breaking elongation are indicators of the material's practical strength. Generally, a larger value indicates superior practical strength.

[0089] (5) Cold resistance: Measured using a Crushberg tester in accordance with JIS K-6773 (1999). The lower the flexibility temperature (°C), the better the cold resistance. The flexibility temperature here refers to the torsional stiffness ratio (3.17 × 10) as specified in JIS in the above measurement. 3 kg / cm 2 This refers to the temperature at which the low-temperature limit is reached. <Evaluation of flexibility temperature> [I]: -30℃ or less [II] Below -25℃ and above -30℃ [III]: Above -25℃

[0090] (6) Heat resistance: Evaluated based on loss due to volatilization and sheet coloration. a) Loss due to volatilization: The mass change of the roll sheet was measured after heating the roll sheet in a gear oven at 170°C for 60 minutes and 120 minutes, and the mass loss rate (mass %) was calculated using the following formula. The smaller the number, the higher the heat resistance. Loss of volatilization (%) = ((Mass before test - Mass after test) / Mass before test) × 100 <Evaluation of loss on volatilization (170°C, 120 minutes)> [I]: Less than 13% [II]: 13% or more but less than 15% [III]: 15% or more b) Sheet coloring: The degree of coloring of the rolled sheets was visually evaluated on a three-point scale after heating them in a gear oven at 170°C for 30 minutes and 60 minutes. <Evaluation of sheet coloring> [I]: No coloring [II]: △Slightly colored [III]: × Colored

[0091] (7) Performance evaluation of polyvinyl chloride resin molded products For performance evaluation of polyvinyl chloride resin molded articles, the results of the evaluation of flexibility temperature, loss of volatilization (170°C, 120 minutes), and sheet coloring are evaluated as follows: if [III] is 1 or higher, it is considered unsuitable; if [II] is 1 or lower (other evaluations are [I]), it is considered good; and if all evaluations are [I], it is considered particularly good.

[0092] (8) Biomass The biomass content of diesters is measured by burning the sample to be measured to generate carbon dioxide, purifying the carbon dioxide in a vacuum line, and then reducing it with hydrogen using iron as a catalyst to produce graphite. This graphite is then processed using a tandem accelerator-based system. 14 It is installed in a dedicated C-AMS device (manufactured by NEC Corporation), 14 The count of C, 13 C's flux ( 13 C / 12 C), 14 C's flux ( 14 C / 12 C) is measured, and from this measurement, the sample carbon relative to standard modern carbon is 14 The percentage of C concentration was calculated. For this measurement, oxalic acid (HOxII), provided by the U.S. National Institute of Standards (NIST), was used as the standard sample.

[0093] [Manufacturing Example 1] In a 2 L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux condenser, 2.00 mol of 4-cyclohexene-1,2-dicarboxylic acid anhydride, 4.80 mol of n-octanol, and 0.4 g of tetraisopropyl titanate (manufactured by Nippon Soda Co., Ltd.) as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 200 °C. The reaction was carried out under reduced pressure, refluxing the alcohol and removing the generated water from the system, until the acid value of the reaction solution reached 0.2 mg KOH / g. After the reaction was complete, the unreacted alcohol was removed from the system under reduced pressure, and then the mixture was neutralized with a 2% NaOH aqueous solution, washed with water, and dehydrated according to a conventional method to obtain 682.5 g of 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl (hereinafter referred to as "ester 1") according to the present invention. The obtained ester 1 had an acid value of 0.01 mg KOH / g, a hue (hazen) of 20, and a biomass content of 66.7%.

[0094] [Manufacturing Example 2] Except for adding n-octanol (3.84 mol), n-dodecanol (0.77 mol), and n-tetradecanol (0.19 mol) instead of n-octanol, the same procedure as in Production Example 1 was followed to obtain 702.0 g of the 4-cyclohexene-1,2-dicarboxylic acid diester mixture according to the present invention (hereinafter referred to as "ester 2"). Each component was quantified by GC analysis using DOP as the standard substance, and the following results were obtained: 64.0 mol% for 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 25.0 mol% for 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-dodecyl, 7.0 mol% for 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, 2.4 mol% for 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 1.4 mol% for 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and 0.2 mol% for 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl. The resulting ester 2 had an acid value of 0.01 mg KOH / g, a hue (Hazen) of 13, and a biomass content of 69.0%.

[0095] [Manufacturing Example 3] The process was carried out in the same manner as in Production Example 1, except that n-octanol (2.40 mol), n-dodecanol (1.87 mol), and n-tetradecanol (0.53 mol) were added instead of n-octanol, to obtain 778.0 g of the 4-cyclohexene-1,2-dicarboxylic acid diester mixture according to the present invention (hereinafter referred to as "ester 3"). Each component was quantified by GC analysis using DOP as the standard substance, and the following were found: 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl 25.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-dodecyl 39.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl 11.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl 15.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl 8.7 mol%, and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl 1.3 mol%. The obtained ester 3 had an acid value of 0.01 mg KOH / g, a hue (Hazen) of 15, and a biomass content of 71.9%.

[0096] [Manufacturing Example 4] Except for adding n-octanol (0.96 mol), n-dodecanol (2.98 mol), and n-tetradecanol (0.86 mol) instead of n-octanol, the same procedure as in Production Example 1 was followed to obtain 871.0 g of the 4-cyclohexene-1,2-dicarboxylic acid diester mixture according to the present invention (hereinafter referred to as "ester 4"). Each component was quantified by GC analysis using DOP as the standard substance, and the following results were obtained: 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl 4.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-dodecyl 25.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl 7.2 mol%, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl 38.0 mol%, 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl 22.0 mol%, and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl 3.2 mol%. The obtained ester 4 had an acid value of 0.01 mg KOH / g, a hue (Hazen) of 11, and a biomass content of 74.4%.

[0097] [Example 1] As the biomass plasticizer of the present invention, biomass plasticizer 1 was obtained by mixing ester 1 obtained in Production Example 1 in a ratio of 95% by mass and epoxidized soybean oil in a ratio of 5% by mass. The biomass content of biomass plasticizer 1 was 68.3%. As described in "(2) Preparation of vinyl chloride press sheet" above, a vinyl chloride resin composition was prepared using biomass plasticizer 1. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0098] [Example 2] As the biomass plasticizer of the present invention, biomass plasticizer 2 was obtained by mixing ester 1 obtained in Production Example 1 in a ratio of 80% by mass with epoxidized soybean oil in a ratio of 20% by mass. The biomass content of biomass plasticizer 2 was 73.2%. Except for using biomass plasticizer 2 instead of biomass plasticizer 1, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0099] [Example 3] As the biomass plasticizer of the present invention, biomass plasticizer 3 was obtained by mixing ester 1 obtained in Production Example 1 in a ratio of 50% by mass with epoxidized soybean oil in a ratio of 50% by mass. The biomass content of biomass plasticizer 3 was 83.2%. Except for using biomass plasticizer 3 instead of biomass plasticizer 1, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0100] [Example 4] As the biomass plasticizer of the present invention, biomass plasticizer 4 was obtained by mixing ester 2 obtained in Production Example 2 in a ratio of 80% by mass and epoxidized soybean oil in a ratio of 20% by mass. The biomass content of biomass plasticizer 4 was 75.0%. Except for using biomass plasticizer 4 instead of biomass plasticizer 1, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0101] [Example 5] As the biomass plasticizer of the present invention, biomass plasticizer 5 was obtained by mixing ester 2 obtained in production example 2 in a ratio of 50% by mass with epoxidized soybean oil in a ratio of 50% by mass. The biomass content of biomass plasticizer 5 was 84.3%. Except for using biomass plasticizer 5 instead of biomass plasticizer 1, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0102] [Example 6] As the biomass plasticizer of the present invention, biomass plasticizer 6 was obtained by mixing ester 3 obtained in Production Example 3 in a ratio of 80% by mass with epoxidized soybean oil in a ratio of 20% by mass. The biomass content of biomass plasticizer 6 was 77.3%. Except for using biomass plasticizer 6 instead of biomass plasticizer 1, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0103] [Example 7] As the biomass plasticizer of the present invention, biomass plasticizer 7 was obtained by mixing ester 3 obtained in Production Example 3 in a ratio of 50% by mass with epoxidized soybean oil in a ratio of 50% by mass. The biomass content of biomass plasticizer 7 was 85.7%. Except for using biomass plasticizer 7 instead of biomass plasticizer 1, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0104] [Comparative Example 1] As a plasticizer, plasticizer 8 was obtained by mixing 20% ​​by mass of ester 1 obtained in production example 1 with 80% by mass of epoxidized soybean oil. The biomass content of plasticizer 8 was 93.2%. As described in "(2) Preparation of vinyl chloride press sheet" above, a vinyl chloride resin composition was prepared using plasticizer 8. Subsequently, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0105] [Comparative Example 2] As a plasticizer, plasticizer 9 was obtained by mixing 20% ​​by mass of ester 2 obtained in production example 2 with 80% by mass of epoxidized soybean oil. The biomass content of plasticizer 9 was 93.6%. Except for using plasticizer 9 instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Comparative Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0106] [Comparative Example 3] As a plasticizer, plasticizer 10 was obtained by mixing 20% ​​by mass of ester 3 obtained in production example 3 with 80% by mass of epoxidized soybean oil. The biomass content of plasticizer 10 was 94.2%. Except for using plasticizer 10 instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Comparative Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 1.

[0107] [Comparative Example 4] A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Comparative Example 1, except that ester 4 obtained in Production Example 4 was used as the plasticizer 11 instead of plasticizer 8. Tensile tests, cold resistance tests, and heat resistance tests were then performed. The results obtained are summarized in Table 1.

[0108] [Comparative Example 5] Except for using DOP as the plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0109] [Comparative Example 6] Except for using DINP as the plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0110] [Comparative Example 7] Except for using DOTH as the plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0111] [Comparative Example 8] Except for using ester 1 as the plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0112] [Comparative Example 9] Except for using ester 2 as the plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0113] [Comparative Example 10] Except for using ester 3 as the plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0114] [Comparative Example 11] Except for using epoxidized soybean oil as a plasticizer instead of plasticizer 8, a vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. The results obtained are summarized in Table 2.

[0115] [Table 1]

[0116] [Table 2]

[0117] Table 1 shows that the biomass plasticizers for vinyl chloride resins according to the present invention, as described in Examples 1 to 7, have a low flexibility temperature of -27°C or lower, a low loss on volatilization (170°C, 120 minutes) of 12.8% or lower, and furthermore, the sheets are uncolored and have a biomass content of 68.3% or higher. [Industrial applicability]

[0118] By replacing the composition of plasticizers for vinyl chloride resins, which are entirely dependent on petroleum-derived plasticizers, with the plant-derived biomass plasticizer for vinyl chloride resins according to the present invention, the amount of petroleum resources used can be reduced, and the environmental burden can be reduced by suppressing carbon dioxide emissions during the production of plasticizers for vinyl chloride resins. The biomass plasticizer for vinyl chloride resins according to the present invention has excellent compatibility with vinyl chloride resins, and therefore offers excellent plasticization efficiency and flexibility, can impart excellent heat resistance and cold resistance, and can be suitably used as a biomass plasticizer for vinyl chloride resins having a specific biomass content. The vinyl chloride resin composition and vinyl chloride resin molded articles, characterized by containing a biomass plasticizer for vinyl chloride resins according to the present invention, can be used as a plasticizer for vinyl chloride resins that has excellent cold resistance and heat resistance and good flexibility. Molded products obtained from the vinyl chloride resin composition containing this plasticizer are extremely useful for applications requiring high levels of cold resistance, heat resistance, and flexibility, such as wire coatings, automotive components, general film sheets (laminates, packaging, vehicles, general merchandise, etc.), agricultural films, leather, compounds, flooring, wallpaper, footwear, sealing materials, textiles, hoses, gaskets, building materials, paints, adhesives, pastes, and medical applications.

Claims

1. (A) Ingredients: General formula (1) 【Chemistry 1】 [In the formula, R １ and R ２ These represent, either identical or different, linear alkyl groups derived from biomass with 8 to 14 carbon atoms. One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by, and (B) Ingredients: Epoxy vegetable oil A biomass plasticizer for vinyl chloride resins containing, A biomass plasticizer for vinyl chloride resins, characterized in that the biomass content of component (A) is 66.7 to 71.9%, and the mass ratio of component (A) to component (B) is 50 to 99% by mass: 1 to 50% by mass.

2. The biomass plasticizer for vinyl chloride resins according to claim 1, wherein component (A) is di-n-octyl 4-cyclohexene-1,2-dicarboxylic acid.

3. The biomass plasticizer for vinyl chloride resins according to claim 1, wherein component (A) is (a) 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, (b) 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-dodecyl, (c) 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, (d) 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, (e) 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and (f) 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl.

4. (A) Components: The sum of (a) to (f) is 100 mol%, and (a):(b):(c):(d):(e):(f) = 20.0 to 67.2 mol%: 19.8 to 40.7 mol%: 5.7 to 11.8 mol%: 1.9 to 15.8 mol%: 1.1 to 9.2 mol%, : 0.1 to 1.4 mol%, the biomass plasticizer for vinyl chloride resins according to claim 3.

5. A vinyl chloride resin composition characterized by containing a vinyl chloride resin and a biomass plasticizer for vinyl chloride resins according to any one of claims 1 to 4.

6. A molded article obtained from the vinyl chloride resin composition described in claim 5.

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